EP3266823B1 - Composition de résine réticulable et fil et câble électrique - Google Patents

Composition de résine réticulable et fil et câble électrique Download PDF

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Publication number
EP3266823B1
EP3266823B1 EP15883995.1A EP15883995A EP3266823B1 EP 3266823 B1 EP3266823 B1 EP 3266823B1 EP 15883995 A EP15883995 A EP 15883995A EP 3266823 B1 EP3266823 B1 EP 3266823B1
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Prior art keywords
hindered amine
stabilizer
resin composition
mass
amine light
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EP3266823A1 (fr
EP3266823A4 (fr
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Kosei Hayashi
Tomohiro Ohseki
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Eneos Nuc Corp
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Eneos Nuc Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Definitions

  • the present invention relates to a crosslinkable resin composition and an electric wire/cable. More specifically, the present invention relates to a crosslinkable resin composition containing an ethylene-based resin and having good electrical insulation properties, and an electric wire/cable obtained by forming, as an insulating coating layer, a crosslinked product of the resin composition on a conductor.
  • insulation coated electric wires/cables for electric power are produced by coating a conductor with a crosslinkable resin composition by extrusion molding, and then crosslinking the crosslinkable resin composition to form an insulating coating layer.
  • crosslinkable resin compositions used in insulation coated electric wires/cables resistance to blooming and color change, scorch resistance, process stability, water-tree resistance, thermal deformation resistance, heat aging resistance, etc. are required.
  • the present applicant has proposed a crosslinkable resin composition containing an ethylene-based resin, a stabilizer, and an organic peroxide, in which a hindered phenol stabilizer, a dialkyl thiodipropionate stabilizer, and a hindered amine stabilizer are used in combination as the stabilizer (refer to, PTL 1 below).
  • the length (production unit) of an electric wire/cable that is continuously produced by extrusion molding is desirably as long as possible.
  • a screen mesh is clogged and blocked by a scorched (partially crosslinked) resin component and a stabilizer having a relatively high viscosity. Consequently, the pressure in the extruder increases, and stable extrusion molding cannot be performed.
  • an extruder for forming an insulating coating layer of a cable is configured so that, when the pressure in the extruder reaches a certain value or more, a limit switch operates to stop the extrusion operation in order to prevent a screen mesh from breaking and to prevent a motor from being overloaded. When the extrusion operation stops, a desired length of the production unit cannot be obtained.
  • the inventors of the present invention have proposed a crosslinkable resin composition that contains 100 parts by mass of an ethylene-based resin, a stabilizer containing 0.001 to 0.5 parts by mass of a hindered amine light stabilizer having a melting point or a glass transition point of 100°C or lower, and 0.5 to 3.0 parts by mass of an organic peroxide, in which molecular weights of all the compounds constituting the stabilizer are each 1,500 or less (refer to, Japanese Patent Application No. 2014-244512 ).
  • crosslinkable resin composition an increase in the pressure does not easily occur in an extruder charged with the crosslinkable resin composition, and an insulating coating layer can be continuously formed by extrusion molding for a long time. Accordingly, an increase in the production unit of an electric wire/cable can be realized.
  • this crosslinkable resin composition has a problem in that the hindered amine light stabilizer, which is a component of the crosslinkable resin composition, is bled out, the content of the hindered amine light stabilizer thereby decreases with time, and, consequently, activity of the organic peroxide maintained by the hindered amine light stabilizer decreases with time. Therefore, this crosslinkable resin composition cannot be stored for a long time.
  • the amount of hindered amine light stabilizer bled out also increases. Therefore, when extrusion molding of such a crosslinkable resin composition is performed, the crosslinkable resin composition slips on a screw. As a result, there may be a problem in that the amount of resin composition extruded (the amount of resin composition discharged) varies, and stable extrusion molding cannot be performed.
  • the present invention has been made in view of the circumstances described above.
  • An object of the present invention is to provide a crosslinkable resin composition which does not easily cause an increase in the pressure in an extruder charged with the crosslinkable resin composition and a variation in the amount of discharge, and with which an insulating coating layer can be continuously and stably formed by extrusion molding for a long time, thereby realizing an increase in the production unit of an electric wire/cable and achieving a good long-term storage property.
  • Another object of the present invention is to provide an electric wire/cable whose production unit can be larger (longer) than that of an electric wire/cable produced using a publicly known crosslinkable resin composition.
  • the crosslinkable resin composition of the present invention bleeding out of the hindered amine light stabilizer (B3) does not easily occur, and thus a good long-term storage property is also obtained.
  • the production unit can be larger (longer) than that of an electric wire/cable produced using a publicly known crosslinkable resin composition.
  • the electric wire/cable (having a long production unit) of the present invention the number of connecting joints between production units can be reduced, and the probability of failure of the electric power system can be significantly reduced.
  • a crosslinkable resin composition of the present invention contains an ethylene-based resin (A), a stabilizer (B) containing a hindered amine light stabilizer (B3), a hindered phenol stabilizer (B1) and a dialkyl thiodipropionate stabilizer (B2), and an organic peroxide (C).
  • Examples of the ethylene-based resin (A) contained in the crosslinkable resin composition of the present invention include, but are not particularly limited to, high-pressure process low-density ethylene homopolymers, high-pressure process low-density ethylene copolymers, high-density ethylene copolymers, medium-density ethylene copolymers, linear low-density ethylene copolymers, and linear very low-density ethylene copolymers.
  • ethylene (co)polymers can be produced by publicly known methods and may be used, as the ethylene-based resin (A), alone or in combination of two or more resins.
  • examples of the polymerization catalyst include radical-generating catalysts such as organic peroxides, azo compounds, and oxygen.
  • examples of the polymerization catalyst include Ziegler catalysts, Phillips catalysts, and metallocene catalysts.
  • Examples of an ⁇ -olefin copolymerized with ethylene in the production of the ethylene-based resin (A) formed of a copolymer include propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, and decene-1.
  • Preferred examples of the ethylene-based resin (A) include high-pressure process low-density ethylene homopolymers, high-pressure process low-density ethylene copolymers, and linear low-density ethylene copolymers, all of which have a density of 0.91 to 0.94 g/cm 3 , in particular, 0.915 to 0.930 g/cm 3 , and a melt mass-flow rate of 0.01 to 10 g/10 min, in particular, 0.5 to 5 g/10 min.
  • An ethylene-based resin having an excessively low melt mass-flow rate has poor processability.
  • an ethylene-based resin having an excessively high melt mass-flow rate is used, the mechanical strength, thermal deformation resistance, circularity, etc. of the insulating coating layer that is finally formed tend to decrease.
  • the stabilizer (B) contained in the crosslinkable resin composition of the present invention contains a hindered amine light stabilizer (B3) as an essential component.
  • Examples of the stabilizer (B) other than the hindered amine light stabilizer (B3) include light stabilizers other than the hindered amine light stabilizer (B3), antioxidants, and process stabilizers.
  • the hindered amine light stabilizer (B3) which is an essential stabilizer (B), is a mixture of a low-molecular-weight hindered amine compound having a molecular weight of 100 to 1,000 and a high-molecular-weight hindered amine compound having a molecular weight of 1,500 to 5,000.
  • Examples of the low-molecular-weight hindered amine compound include compounds represented by general formula (1) below, and dimers to tetramers of the compounds (in this case, R 1 represents a divalent to tetravalent group). These may be used alone or in combination of two or more compounds.
  • the low-molecular-weight hindered amine light stabilizer has a molecular weight of 100 to 1,000, and preferably 400 to 900.
  • the low-molecular-weight hindered amine light stabilizer include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracalboxylate (LA-52, manufactured by ADEKA Corporation), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (LA-87, manufactured by ADEKA Corporation), and bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (LA-77, manufactured by ADEKA Corporation or TINUVIN 770, manufactured by BASF). These may be used alone or in combination of two or more compounds.
  • Examples of the high-molecular-weight hindered amine compound include compounds represented by general formulae (2) to (6) below. These may be used alone or in combination of two or more compounds.
  • R 1 represents a monovalent group represented by [where X represents a monovalent group represented by (where R 3 to R 7 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms].
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 1 and R 2 each represent an alkylene group having 1 to 8 carbon atoms
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • the high-molecular-weight hindered amine light stabilizer has a molecular weight (weight-average molecular weight when two or more compounds are used in combination) of 1,500 to 5,000, and preferably 2,000 to 4,000.
  • a resin composition obtained by using, as the hindered amine light stabilizer (B3), a low-molecular-weight hindered amine compound and a high-molecular-weight hindered amine compound in combination does not easily cause an increase in the pressure in an extruder charged with the resin composition and a variation in the amount of discharge.
  • an insulating coating layer can be continuously and stably formed by extrusion molding for a long time.
  • the resulting resin composition also has a good long-term storage property.
  • a ratio of the high-molecular-weight hindered amine compound to the hindered amine light stabilizer (B3) is preferably 30% to 60% by mass.
  • the high-molecular-weight hindered amine compound and the low-molecular-weight hindered amine compound are mixed in a balanced manner. Consequently, both an increase in the pressure in an extruder charged with the resulting resin composition and a variation in the amount of discharge can be reliably suppressed. Furthermore, good extrusion stability can be exhibited, and the resulting resin composition has a good long-term storage property.
  • the hindered amine light stabilizer (B3) contained in the crosslinkable resin composition of the present invention has a reduced viscosity of 3.5 to 5.5 cm 3 /g, preferably 3.9 to 5.4 cm 3 /g measured at a temperature of 40°C in accordance with ISO 1628-1 or JIS K 7367-1.
  • the hindered amine light stabilizer (B3) has a reduced viscosity of 2.0 to 3.5 cm 3 /g, preferably 2.5 to 3.5 cm 3 /g measured at a temperature of 110°C in accordance with ISO 1628-1 or JIS K 7367-1.
  • hindered amine light stabilizer when the reduced viscosity at 40°C exceeds 5.5 cm 3 /g or the reduced viscosity at 110°C exceeds 3.5 cm 3 /g, such a hindered amine light stabilizer having a high viscosity causes clogging (blocking) of a screen mesh in an extruder, resulting in an increase in the pressure in the extruder. Thus, extrusion molding cannot be performed for a long time (refer to Comparative Examples 4 and 5 and Comparative Examples 7 and 8 described below).
  • a hindered amine light stabilizer having a reduced viscosity at 40°C of less than 3.5 cm 3 /g or a reduced viscosity at 110°C of less than 2.0 cm 3 /g easily causes bleeding out.
  • a resin composition containing such a stabilizer the amount of discharge during extrusion molding varies and extrusion stability is impaired (refer to Comparative Examples 1 and 2 described below), or long-term storage property is impaired (refer to Comparative Examples 3 and 6 described below).
  • the weight-average molecular weight (Mw) of the hindered amine light stabilizer (B3) contained in the crosslinkable resin composition of the present invention is preferably 700 to 2,300, and more preferably 900 to 2,100.
  • the weight-average molecular weight (Mw) of the hindered amine light stabilizer (B3) which is a mixture of at least one low-molecular-weight hindered amine compound and at least one high-molecular-weight hindered amine compound, is a calculated value determined by the formula below from molecular weights (M i ) and molar fractions (n i ) of the hindered amine compounds constituting the mixture.
  • Mw ⁇ n i M i 2 / ⁇ n i M i
  • the hindered amine light stabilizer (B3) having a weight-average molecular weight (Mw) of 700 or more, in particular, 900 or more does not easily cause bleeding out.
  • a resin composition containing such a hindered amine light stabilizer (B3) has a good long-term storage property. Furthermore, a variation in the amount of the resin composition discharged from an extruder charged with the resin composition is small, and thus the resin composition has good extrusion stability.
  • a rate of increase in the pressure in an extruder charged with the resin composition is low, and extrusion molding can be performed for a long time.
  • the content of the hindered amine light stabilizer (B3) in the crosslinkable resin composition of the present invention is 0.001 to 0.5 parts by mass, preferably 0.003 to 0.1 parts by mass, and more preferably 0.005 to 0.02 parts by mass relative to 100 parts by mass of the ethylene-based resin (A).
  • a resin composition that does not contain the hindered amine light stabilizer (B3) or that has an excessively low content of the hindered amine light stabilizer (B3) cannot be stored for a long time because activity of an organic peroxide (C) described below significantly decreases with time. Furthermore, water produced by secondary degradation of the organic peroxide (C) increases and electrical properties (insulating properties) are impaired (refer to Comparative Example 9 described below).
  • the crosslinkable resin composition of the present invention contains a stabilizer (B) other than the hindered amine light stabilizer (B3) including a hindered phenol stabilizer (B1) and a dialkyl thiodipropionate stabilizer (B2).
  • a stabilizer (B) other than the hindered amine light stabilizer (B3) including a hindered phenol stabilizer (B1) and a dialkyl thiodipropionate stabilizer (B2).
  • Examples of the hindered phenol stabilizer (B1) include compounds having a hindered phenol structure and having a molecular weight of 1,500 or less.
  • hindered phenol stabilizer (B1) examples include 4,4'-thiobis-(3-methyl-6-t-butylphenol) (SEENOX BCS, manufactured by Shipro Kasei Kaisha, Ltd.), 4,4'-thiobis-(6-t-butyl-o-cresol) (ETHANOX 736, manufactured by Ethyl Corporation), tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane (Irganox 1010, manufactured by BASF), N,N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine (Irganox 1024, manufactured by BASF), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid (Cyanox 1790, manufactured by CYTEC Industries Inc.), 1,3,3,5
  • the content of the hindered phenol stabilizer (B1) is preferably 0.01 to 1.0 part by mass, and more preferably 0.02 to 0.5 parts by mass relative to 100 parts by mass of the ethylene-based resin (A).
  • dialkyl thiodipropionate stabilizer (B2) examples include compounds having an alkyl group with 10 to 20 carbon atoms and having a molecular weight of 1,500 or less.
  • dialkyl thiodipropionate stabilizer (B2) which is an optional stabilizer (B)
  • dialkyl thiodipropionate stabilizer (B2) which is an optional stabilizer (B)
  • DLTP dilauryl thiodipropionate
  • DSTP distearyl thiodipropionate
  • DMTP dimyristyl thiodipropionate
  • the content of the dialkyl thiodipropionate stabilizer (B2) is preferably 0.005 to 0.6 parts by mass, and more preferably 0.01 to 0.3 parts by mass relative to 100 parts by mass of the ethylene-based resin (A).
  • Examples of the organic peroxide (C) contained in the crosslinkable resin composition of the present invention include publicly known compounds used as a crosslinking agent of ethylene-based resins.
  • organic peroxide (C) examples include di-t-butyl-peroxide, 1,1-bis-t-butyl-peroxybenzoate, 2,2-bis-t-butyl-peroxybutane, t-butyl-peroxybenzoate, dicumylperoxide, 2,5-dimethyl-2,5-di-t-butyl-peroxyhexane, t-butyl-cumylperoxide, and 2,5-dimethyl-2,5-di-t-butyl-peroxyhexyne-3. These may be used alone or in combination of two or more compounds.
  • the content of the organic peroxide (C) in the crosslinkable resin composition of the present invention is usually 0.5 to 3.0 parts by mass, and preferably 1.0 to 2.5 parts by mass relative to 100 parts by mass of the ethylene-based resin (A).
  • the insulating coating layer that is finally formed has poor thermal deformation resistance.
  • the resulting crosslinkable resin composition has poor scorch resistance.
  • the crosslinkable resin composition of the present invention may contain an olefin-based resin other than the ethylene-based resin (A), various additives, and auxiliary materials as long as characteristics of the resin composition of the present invention are not impaired according to the purpose of use.
  • olefin-based resins serving as the optional components include ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-maleic acid copolymers, ethylene-diene compound copolymers, ethylene-vinylsilane copolymers, maleic anhydride grafted ethylene-based polymers, acrylic acid grafted ethylene-based polymers, and silane grafted ethylene-based polymers.
  • additives and the auxiliary materials serving as the optional components include a stabilizer other than the stabilizer (B) described above, a processability improver, a dispersant, a copper inhibitor, an antistatic agent, a lubricant, carbon black, a crosslinking aid such as triallyl cyanurate, and an antiscorching agent such as ⁇ -methylstyrene dimer.
  • the crosslinkable resin composition of the present invention can be prepared by mixing the essential components [ethylene-based resin (A), the stabilizer (B), and the organic peroxide (C)] and the optional components at a particular ratio, kneading the resulting mixture, and granulating the mixture.
  • the crosslinkable resin composition of the present invention is preferably provided in the form of pellets having an average particle size of about 2 to 7 mm from the viewpoint of the ease of engaging in a screw of an extruder, handleability, and the like.
  • Examples of the method for producing a pelletized crosslinkable resin composition include
  • An electric wire/cable of the present invention includes a conductor and an insulating coating layer that covers the conductor, the insulating coating layer being formed by crosslinking the crosslinkable resin composition of the present invention, that is, the insulating coating layer being formed of a crosslinked product of the resin composition.
  • the electric wire/cable of the present invention can be produced by covering a conductor that is mainly formed of copper or aluminum with the crosslinkable resin composition of the present invention by extrusion molding, and crosslinking the crosslinkable resin composition to form an insulating coating layer.
  • a conductor in general, in a case of a low-voltage cable, a conductor is covered with only a single layer using a single-layer extruder.
  • a conductor is covered with a laminate including a first layer formed of an inner semi-conducting layer resin composition, a second layer formed of the crosslinkable resin composition of the present invention, and a third layer formed of an outer semi-conducting layer resin composition using a three-layer extruder at a temperature that is equal to or higher than a melting point of each resin but is lower than a decomposition temperature of the organic peroxide (C).
  • the resin composition is crosslinked by performing heating at a temperature equal to or higher than the decomposition temperature of the organic peroxide (C) in an atmosphere of nitrogen, water vapor, silicone oil, a molten salt, or the like.
  • the cables can be produced.
  • the electric wire/cable of the present invention has good properties such as mechanical properties, electrical properties (insulating properties of the coating layer), and long-term storage properties. Furthermore, during the production of the electric wire/cable (extrusion molding step), an increase in the pressure in an extruder and a variation in the amount of discharge are small, and stable extrusion molding can be continuously performed for a long time.
  • ethylene-based resins, stabilizers, and organic peroxides used for producing resin compositions of Examples and Comparative Examples are as follows.
  • Reduced viscosities of each of stabilizers described below and hindered amine light stabilizer (B3), which are mixtures of stabilizers, were determined in accordance with ISO 1628-1 or JIS K7367-3 (2002) by diluting the stabilizer (mixture) with xylene to prepare diluted solutions having different concentrations, measuring dynamic viscosities at 40°C and 110°C with a capillary viscometer, and then converting the dynamic viscosities to reduced viscosities.
  • a crosslinkable resin composition of the present invention was obtained as in Example 1 except that a mixture of 0.0025 parts by mass of the stabilizer (B3-1) and 0.0025 parts by mass of the stabilizer (B3-3) was used as the hindered amine light stabilizer (B3) in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition of the present invention was obtained as in Example 1 except that a mixture of 0.002 parts by mass of the stabilizer (B3-1) and 0.003 parts by mass of the stabilizer (B3-3) was used as the hindered amine light stabilizer (B3) in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition of the present invention was obtained as in Example 1 except that a mixture of 0.01 parts by mass of the stabilizer (B3-1) and 0.01 parts by mass of the stabilizer (B3-3) was used as the hindered amine light stabilizer (B3) in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition of the present invention was obtained as in Example 1 except that a mixture of 0.0025 parts by mass of the stabilizer (B3-2) and 0.0025 parts by mass of the stabilizer (B3-3) was used as the hindered amine light stabilizer (B3) in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.02 parts by mass of the stabilizer (B3-1) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.01 parts by mass of the stabilizer (B3-1) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.005 parts by mass of the stabilizer (B3-1) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that a mixture of 0.0015 parts by mass of the stabilizer (B3-1) and 0.0035 parts by mass of the stabilizer (B3-3) (mixture having excessively high reduced viscosities at 40°C and 110°C) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.005 parts by mass of the stabilizer (B3-3) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.005 parts by mass of the stabilizer (B3-2) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that a mixture of 0.0025 parts by mass of the stabilizer (B3-1) and 0.0025 parts by mass of the stabilizer (B3-4) (mixture having excessively high reduced viscosities at 40°C and 110°C) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that 0.005 parts by mass of the stabilizer (B3-4) was used as a hindered amine light stabilizer in accordance with the formula shown in Table 1 below.
  • a crosslinkable resin composition for comparison was obtained as in Example 1 except that no hindered amine light stabilizer was mixed in accordance with the formula shown in Table 1 below.
  • An alternating-current voltage of 1 kV/1,000 Hz was applied to the sheet using a water electrode for 500 hours.
  • the sheet was then sliced in the thickness direction to have a size of about 0.1 mm to prepare 10 sliced pieces.
  • the sliced pieces were immersed in a methylene blue staining solution and stained.
  • the stained sliced pieces were observed with an optical microscope, and whether or not a water tree was generated was examined. When the generation of a water tree was not observed, the resin composition was evaluated as acceptable (A). When the generation of a water tree was observed, the resin composition was evaluated as unacceptable (B).
  • an insulating coating layer can be continuously and stably formed by extrusion molding for a long time, and an increase in the production unit of an electric wire/cable can be realized.
  • crosslinkable resin compositions each have a small amount of water production and good water-tree resistance, and thus are suitable as insulating coating materials of an electric wire/cable.
  • the resin compositions obtained in Comparative Examples 1 and 2 each contain only a low-molecular-weight hindered amine compound as a hindered amine light stabilizer.
  • the reduced viscosities of the hindered amine light stabilizer at 40°C and 110°C are excessively low.
  • each of the resin compositions has a large torque variation and has poor extrusion stability.
  • the resin compositions obtained in Comparative Examples 3 and 6 each contain only a low-molecular-weight hindered amine compound as a hindered amine light stabilizer.
  • the reduced viscosities of the hindered amine light stabilizer at 40°C and 110°C are excessively low.
  • the resin compositions have poor long-term storage properties.
  • the resin compositions obtained in Comparative Examples 5 and 8 each contain only a high-molecular-weight hindered amine compound as a hindered amine light stabilizer.
  • the reduced viscosities of the hindered amine light stabilizer at 40°C and 110°C are excessively high.
  • the rate of increase in the pressure in the extruder charged with the resin composition is high, and the resin composition has poor extrusion stability.
  • the crosslinkable resin composition obtained in Comparative Example 9 contains no hindered amine light stabilizer and thus has a poor long-term storage property and poor water-tree resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Claims (5)

  1. Composition de résine réticulable comprenant 100 parties en masse d'une résine à base d'éthylène (A) ; un stabilisant (B) contenant de 0,001 à 0,5 partie en masse d'un photostabilisant à amine encombrée (B3) ; et de 0,5 à 3,0 parties en masse d'un peroxyde organique (C),
    le stabilisant (B) contenant en outre un stabilisant à phénol encombré (B1) et un stabilisant à base de thiodipropionate de dialkyle (B2) en plus du photostabilisant à amine encombrée (B3),
    le photostabilisant à amine encombrée (B3) étant un mélange d'un composé à amine encombrée à bas poids moléculaire ayant un poids moléculaire de 100 à 1000 et d'un composé à amine encombrée à haut poids moléculaire ayant un poids moléculaire de 1500 à 5000, et
    le photostabilisant à amine encombrée (B3) ayant une viscosité réduite de 3,5 à 5,5 cm3/g mesurée à une température de 40 °C et une viscosité réduite de 2,0 à 3,5 cm3/g mesurée à une température de 110 °C conformément à l'ISO 1628-1 ou la JIS K7367-1.
  2. Composition de résine réticulable selon la revendication 1, dans laquelle le photostabilisant à amine encombrée (B3) a un poids moléculaire moyen en poids (Mw) de 700 à 2300.
  3. Composition de résine réticulable selon la revendication 1 ou 2, dans laquelle un rapport du composé à amine encombrée à haut poids moléculaire au photostabilisant à amine encombrée (B3) va de 30 % à 60 % en masse.
  4. Composition de résine réticulable selon la revendication 1 comprenant :
    100 parties en masse d'une résine à base d'éthylène (A) ;
    0,01 à 1,0 partie en masse d'un stabilisant à phénol encombré (B1) ;
    0,005 à 0,6 partie en masse d'un stabilisant à base de thiodipropionate de dialkyle (B2) ;
    0,001 à 0,5 partie en masse d'un photostabilisant à amine encombrée (B3) ; et
    0,5 à 3,0 parties en masse d'un peroxyde organique (C),
    le photostabilisant à amine encombrée (B3) étant un mélange de 40 % à 70 % en masse du composé à amine encombrée à bas poids moléculaire et de 60 % à 30 % en masse du composé à amine encombrée à haut poids moléculaire, le photostabilisant à amine encombrée (B3) ayant une viscosité réduite de 3,9 à 5,4 cm3/g mesurée à une température de 40 °C et une viscosité réduite de 2,5 à 3,5 cm3/g mesurée à une température de 110 °C conformément à l'ISO 1628-1 ou la JIS K7367-1, et
    le photostabilisant à amine encombrée (B3) ayant un poids moléculaire moyen en poids (Mw) de 900 à 2100.
  5. Fil/câble électrique comprenant un conducteur ; et une couche de revêtement isolante qui recouvre le conducteur, la couche de revêtement isolante étant formée en réticulant la composition de résine réticulable selon l'une quelconque des revendications 1 à 4.
EP15883995.1A 2015-03-05 2015-08-11 Composition de résine réticulable et fil et câble électrique Active EP3266823B1 (fr)

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WO2019121725A1 (fr) * 2017-12-18 2019-06-27 Borealis Ag Composition réticulable contenant des antioxydants et présentant une formation réduite de méthane après réticulation, et article
JP7451405B2 (ja) * 2017-12-18 2024-03-18 ボレアリス エージー 酸化防止剤を含む架橋性組成物、並びにメタン形成及び物品
WO2019121735A1 (fr) 2017-12-18 2019-06-27 Borealis Ag Câble constitué d'une composition réticulable comprenant des antioxydants, et formation de méthane bénéfique
KR102294987B1 (ko) 2020-03-27 2021-08-30 도레이첨단소재 주식회사 내후성이 강화된 부직포와 그의 적층체, 및 물품
CN116848189A (zh) * 2021-02-23 2023-10-03 韩华思路信株式会社 具有优异的可加工性的用于超高压电缆的半导体树脂组合物、及其制备方法
CN118294285B (zh) * 2024-06-03 2024-09-13 北京智慧能源研究院 一种电缆绝缘料长时挤出稳定性测试装置及评价方法

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KR20170051485A (ko) 2017-05-11
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TWI583731B (zh) 2017-05-21
US20170362411A1 (en) 2017-12-21
JP2016160402A (ja) 2016-09-05
EP3266823A1 (fr) 2018-01-10
CN107001726A (zh) 2017-08-01
EP3266823A4 (fr) 2018-01-10
KR101855637B1 (ko) 2018-05-04

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